Anthropogenic
Geoch
hemiistry
t
(1) Local – Regional – Global scale emissions
((2)) Types
yp of emissions:
• solid waste
• liquid waste
waste
• acid mine drainage
• volatile emissions
phere
• fine particle emissions to the atmosp
• “natural pollution”,
e g arsenic in Bangladesh well
e.g.
waters.
Anthropogenic geochemistry
3) Regional and global scale anthropogenic emissions.
some elements of particular interest:
• Lead (Pb): globally
globally, the most anthropogenically
enhanced element; emitted to the atmosphere by high
temp
perature industrial p
processes (smelting,
g, coal
combustion, etc.) and by automobiles using leaded
gasoline.
• Mercury (Hg): one of the most volatile toxic
elements; emitted from high temperature industrial
activities (similar to lead); exists in toxic organic mercury
compounds Also used in industrial processing and gold
compounds.
mining, released into natural waters. Mercury is high in
fish in lakes located downwind of coal combustion
regions. It bioaccumulates in predatory fish such as
salmon and swordfish.
Anthropogenic geochemistry
Hg,
g, continued: “Minamata Bayy Disease” from industrial mercury
y
release into a fished harbor is one of the most infamous
pollution episodes. Minamata is a small town in Japan facing an
ocean embayment
embayment. From 1932 to 1968
1968, a company dumped
approximately 27 tons of mercury compounds into the bay.
p who ate fish from the bay
y develop
ped
Thousands of people
symptoms of methyl mercury poisoning.
• Cadmium (Cd): also volatile and used in industrial
activities (Ni-Cd batteries; Cd-plated metals, etc.). “Itai-Itai”
disease is perhaps the second most infamous pollution
episodes. In the early years of the 20th century, villagers along
the Jinzu River basin in Japan developed a painful disease that
was dubbed “Itai-Itai” (“it hurts, it hurts”)). Research didn’t begin
until the 1950s when and in May 1968 it was determined that it
was due to chronic cadmium poisoning caused by commercial
mining operations. It impairs kidney function and leads to
calcium deficiency and brittle bones.
Cd in toys
Toxic
o c metal
eta found
ou d in kids'
ds je
jewelry
e y very
e y dangerous
da ge ous
By JUSTIN PRITCHARD
The Associated Press
Sunday,
y, Januaryy 10,, 2010;; 2:26 PM
-- Cadmium is a soft, whitish metal that occurs naturally in soil. It's perhaps best known as one half of rechargeable nickel-cadmium batteries, but also is used in pigments, electroplating and plastic.
Lab testing organized by The Associated Press shows that it also is present in children's jewelry - sometimes at eye­
poppiing levels
l exceedi
ding 90 percentt off th
the ititem''s ttotal
t l weight.
i ht
Most people get a microscopic dose of the heavy metal just by breathing and eating. Plants, including tobacco, take up
cadmium through their roots and people absorb it during digestion or inhalation. Without direct exposure, however, people usually don't experience its nasty side: cancer, kidneys that leak vital protein, bones that spontaneously snap.
C d i
Cadmium
iis particularly
ti l l d
dangerous ffor children
hild
b
because growing
i b
bodies
di readily
dil absorb
b b substances,
b t
and
d cadmium
d i
accumulates in the kidneys for decades.
"Just small amounts of chemicals may radically alter development," said Dr. Robert O. Wright, a professor at Harvard University's medical school and school of public health. "I can't even fathom why anyone would allow for even a small amount to be accessible
accessible.
"
"
Recent research by Wright found that as cadmium exposure increased, kids were more likely to report learning disabilities.
Dr. Aimin Chen of the University of Cincinnati's medical school also has studied how cadmium affects young brains. While lead
Whil
d iis th
the heavy mettall mostt associat
i ted
d with
ith h
harming
i cogniti
itive devellopment,
t Ch
Chen h
has conclluded
d d th
thatt cad
dmium
i
lowers IQ even more than lead - though cadmium isn't harming the average American child because the typical
exposure is not as large as lead.
Scientists don't know how much cadmium it takes to kill a child. The only child's death attributed to cadmium that AP
found was a nearly 3
3-year-old
year old boy from Toronto
Toronto. According to a case study published in 1994
1994, an autopsy showed his
brain had swollen; the researchers concluded his exposure came from items around his home such as paint pigments,
batteries or cadmium-electroplated utensils.
Anthropogenic Geochemistry
• Nitrogen – as NO3-, usually from fertilizers. Too much nitrate in waters
damages infant’s brain development. It also can lead to “eutrophication” of
coastal seawaters (e.g. Gulf of Mexico “dead zone”).
• Phosphorus – as PO43- usually from fertilizers now (although also from
detergents in the past). Can lead to “eutrophication” of lakes and rivers.
• Selenium - Human selenosis at the population level is rare and is generally
related to excesses from food rather than from drinking water. It has been
reported from China and Venezuela where selenium-rich
selenium rich food is grown and
consumed locally (Tan, 1989; WHO, 1996). Cancers of the skin and
pancreas have been attributed to high selenium intake (Vinceti et al., 1998).
poos and is potentially
y
Selenium sulfide is used in antidandruff shamp
carcinogenic but is not absorbed through the skin unless there are lesions
(WHO, 1987). Selenium toxicity can lead to hair and nail loss and disruption
of the nervous and digestive systems in humans and to alkali disease in
animals. Chronic selenosis in animals is not common but has been reported
from parts of Australia, China, Ireland, Israel, Russia, South Africa, USA,
and Venezuela (Oldfield, 1999). Liver damage is a feature of chronic
selenosis in animals (WHO, 1987). Source: Plant, J. A., Kinniburgh, D. G., Smedley, P.
L., Fordyce, F. M. & Klinck, B. A. in Treatise on Geochemistry Vol. 9 (eds. Holland, H. D. & Turekian,
K. K.) (Elsevier, Amsterdam, 2004).
Kesterson Reservoir, Central California
•
One of the best-documented cases of selenium toxicity in animals occurred at Kesterson Reser­
voir, California, USA (Jacobs, 1989; Wu et al., 2000). Soil irrigation in the western San Joaquin
Valley of California began in the late 1800s and accelerated, particularly in the 1930s – 1940s.
Irrigation water was taken from both surface water and groundwater (Deverel
(Deverel and Fujii
Fujii,, 1988).
During the 1970s, flow into the reservoir was mainly surface water, but over the period 1981 –
1986 almost all the inflow was from shallow agricultural drainage for which the reservoir acted as
a set of evaporation ponds. This inflow contained 250 – 350 mg L selenium, mostly present as
bioavailable selenate (Se(VI)). The primary source of the selenium is believed to have been
pyrite in shales, particularly the Upper Cretaceous – Paleocene Moreno Shale and the Eocene –
Oligocene Kreyenhagen Shale. Concentrations of selenium in these formations range up to 45
mg kg, median concentrations being 6.5 mg kg and 8.7 mg kg, respectively (Presser, 1994). The
concentration of selenium in the surface sediments (0 – 0.3 m depth) of the old playas is in the
range 1 – 20 mg kg reflecting the historical accumulation of selenium from the selenium-rich
selenium rich
drain water. Deeper sediments typically contain much lower selenium concentrations of 0.1 – 1
mg kg (Tokunaga et al., 1994). Between 1983 and 1985, the USA Wildlife Service compared the
biological impact of the high selenium in the Kesterson Reservoir region to that of the adjacent
Volta Wildlife area, which was supplied with water containing normal selenium concentrations.
The research showed that the high concentrations of selenium in the irrigation waters were
having a detrimental effect on the health of fish and wildlife (Tokunaga et al., 1994). Health
effects on birds in the Kesterson Reservoir area were very marked. Twenty-two percent of the
eggs contained dead or deformed embryos. The developmental deformities included missing or
abnormal eyes, beaks, wings, legs, and feet as well as hydrocephaly. It has been estimated that
at least 1,000 adult and young birds died between 1983 and 1985 as a result of consuming
plants and fish containing 12 – 120 times the normal amount of selenium. No overt adverse
health effects were noted in reptile or mammalian species, but the concentrations of selenium
present were of concern in terms of bioaccumulation through the food chain
chain.
Source: Plant, J. A., Kinniburgh, D. G., Smedley, P. L., Fordyce, F. M. & Klinck, B. A. in Treatise
on Geochemistry Vol. 9 (eds. Holland, H. D. & Turekian, K. K.) (Elsevier, Amsterdam, 2004).
Acid Mine Drainage
• Pyrite oxidation:
=
+
2 FeS2 + 15/2 O2 + 4 H2
2O --> Fe2O3 + 4 SO4 + 8 H
• Sulfide ores are common sources of Fe, Zn, Cd, and H2SO4. Coal
deposits often contain sulfide minerals
minerals, so acid mine drainage
commonly affects both sulfide ore and coal tailings (the waste leftover
after mining).
• Acidic waters are in themselves damaging to organisms (e.g. fish do
not live in low-pH waters, perhaps because of enhanced aluminum
solubility at low pH)
pH). The low pH can also mobilize toxic trace metals
such as Cd, As, and Pb.
• Example: Rio Tinto mining complex (Spain): drains into pH ~ 2 rivers
that enter the Atlantic coastal waters of southern Spain having more
than a millionfold more Zn than normal ocean surface waters, along
with
ith other
th metals
t l such
h as Pb
Pb, Cd
Cd, and
dA
As. Thi
This effluent
ffl
t can b
be ttraced
d
into the Mediterranean Sea.
Rio Tinto picture
Rio Tinto Pb
pollution
The Global Anthropogenic Lead Experiment
• Lead is a volatile element and it is emitted by
by
high temperature industrial activities
(smelting coal combustion,
(smelting,
combustion incineration,
incineration
cement manufacture).
• Leaded gasoline utilization creates fine
particles that the atmosphere transports to
gions of the world.
remote reg
• Most of the lead in the present ocean derives
from human activities.
• Changes in the patterns of industrial and
gasoline Pb emissions have led to timedependent changes for oceanic lead during
the past 180 years.
Anthropogenic Pb – how we use Pb and release it into the environment
•
•
•
•
•
•
•
•
•
••
•
Automobile batteries
Solder – electronics and pipe sealing
Cathode ray tubes
PVC stabilizer
Wine bottle seals
High temperature industrial activities
(smelting, coal burning, etc.)
I i
Incinerati
tion
-------------------------“Tin”
“Tin” can solder seams
Gasoline anti-knock compound
House paint
Water pipes
Health effects of lead
• Pb++ interferes with Ca++ biochemistry.
biochemistry
• Ca++ is used extensively in intra- and inter-cellular
electrical messaging
messaging.
• At high levels, Pb causes extreme and permanent
mental and physical damage.
• Damage to workers at tetraethyl Pb plant gave it the
ywayy New Jerseyy:
moniker “looneyy gas” (1924,, Bay
80% of staff die or suffer severe Pb poisoning).
• A study of the achievement, behavior, and baby tooth
Pb content of children in Somerville MA (Needleman
et al. 1979) showed a strong (negative) correlation
between Pb and behavioral indices with no evidence
of a threshold.
studies
• Subsequent detailed medical and biochemical studies
have elucidated the pathways of Pb’s effects on
humans.
Clair Patterson and Lead
Pb in Camp Century Greenland Ice Core
Pb
(µg/kg)
1800
1900
Age (yr A.D.)
Pb in the human environment according to Patterson:
• Some off th
the uses off lead
d have
h
increased
d Pb iin aiir, food
d
and water by orders of magnitude above prehistoric levels.
• Pb in ancient Peruvian bones is orders of magnitude lower
than those of modern humans.
10,000
000 times
• Pb in (lead soldered) canned tuna fish is 10
higher than tuna when they are caught.
gher
• Modern nearshore marine sediments show much hig
Pb concentrations than those deposited 100’s of years ago.
• Leaded gasoline and high temperature industrial activities
have spread
d llead
d to remotte regiions. Human actitiviti
ities have
increased the flux of lead into the earth surface
environment by more than a factor of ten.
• The typical individual in the U.S. in the middle of the 20th
century was within an order of magnitude of demonstrated
toxic levels.
Pb in the human environment according to the lead industry:
• Lead isn’t
isn t a problem (except maybe at very extreme
exposures).
Patterson’s
s data are wrong: Pb in food and water isn’t
isn t
• Patterson
any different than it was in pre-industrial times.
y of • Volcanoes and other natural sources emit plenty
lead. How could humans emit more than they do?
• Even if it is a problem, it isn’t our fault.
• Can you prove it was my lead that caused your
problem?
Other Pb industry responses to Patterson:
• Representatives of the Ethyl corporation
corporation, in
Patterson's words, tried to "buy me out through
pp
that would yield results favorable to
research support
their cause.”
• Instead of joining forces with Ethyl, Patterson
delilivered
d a lecture
t
assaili
iling th
the company''s acti
tiviti
ities
and predicting the demise of their TEL operation.
• Following these events,
events his longstanding contract
contract
with the Public Health Service was not renewed, nor
was a substantial contract with the American
American
Petroleum Institute.
• Members of the board of trustees at Cal Tech leaned
on the chairman of his department to fire him. Others
have alleged that Ethyl offered to endow a chair at
Cal Tech if Patterson was sent packing
packing.
(J. Kitman, The Nation, March 20,
2000)
Pb in lunch boxes
August 31, 2005
A Back to School Warning: Children
Children’s
s Vinyl Lunch Boxes Can Contain
Contain
Dangerous Levels of Lead
Oakland, CA – The Center for Environmental Health (CEH) announced it is filing
Oakland
lawsuits today against makers and retailers of soft vinyl lunch boxes that can expose
children to harmful levels of lead. The Center has also notified several other companies
of violations under California’s toxics law Prop
position 65 (Prop
p 65)) for lunch boxes with
high lead levels. The lawsuits and violation notices against companies including Toys
“R” Us, Warner Brothers, DC Comics, Time Warner, Walgreens, and others involve
many lunch boxes featuring beloved children’s characters including Superman, Tweety
Bird, Powerpuff
ff Girls,
G
and Hamtaro. The level off lead in one lunch box, an Angela
Anaconda box made by Targus International, tested at 56,400 parts per million (ppm)
of lead, more than 90 times the 600 ppm legal limit for lead in paint in children’s
products.
products
In most cases, the highest lead levels were found in the lining of lunch boxes, where lead could come into
direct contact with food. Lead is known to be harmful to children even in minute amounts,, as it can imp
pair
brain development and cause other behavioral and developmental problems. Children may be exposed to
lead from lunch boxes when they eat food that has been stored in them. Handling the lunchboxes just
before eating could also be an exposure risk.
It is not possible to tell by appearance whether a vinyl lunch box may contain lead, so CEH is advising
parents to avoid vinyl lunch boxes altogether.
This image has been removed due to copyright restrictions.
Figure 2. Flegal et al., 1983
Courtesy Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
Global gas and Pb gas consumption, 1992
This image has been removed due to copyright restrictions.
Please see the pie charts showing global gas and Pb gas consumption in 1992.
Thomas, V. M. "The Elimination of Lead in Gasoline." Ann Rev Energy Environ 20 (1995): 301-24.
Surface Water Pb in the Western North Atlantic is still decreasing!
Meridional Pb section in the Western North Atlantic (2002, 2005)
North
South
Pb
Pb,
pmol/kg
ODV graphics
Pb in the
Indian
Ocean,
2010
Image courtesy of NOAA.
x-rayy imag
ge of a coral core slab
Pb
b isotopes
sotopes
206Pb
=>
(24.1%)
35U =>
207
0 Pb
• 235
(22.1%)
208Pb
• 232Th =>
(52 4%)
(52.4%)
• Solar nebula => 204Pb (
1.4%)
•
238U
Lima et al. (2005)
Anthropogenic
p
in
Lead deposition
the Northeast U.S.
(past 250 yyears))
(p
Pettaquamscutt
Estuary Rhode
Estuary,
Island, USA (near URI
Graduate School of
Oceanography): a
permanently anoxic
estuary with varved
sediments
(established by 137Cs,
Cs
14C, and 210Pb: Lima,
King, et al., Geochim.
Cosmochim. Acta .)
Lima et al. (2005)
The Upper Mississippi Valley District
dominated lead mining in the middle of the
19th century, because the ores were near the
surface,
f
were easily
il processed
db
by 1
1-2
2 person
operations (charcoal kilns), and were near
appropriate transportation (Mississippi River
system).
Prevailing winds
Pettaquamscut
t, Saanich Pb
isotope
records, 1800­
2000
• N
Note
t th
the very rapid
id d
decrease in 206Pb/207Pb att
1909. What caused this event?
MIT OpenCourseWare
http://ocw.mit.edu
12.119 Analytical Techniques for Studying Environmental and Geologic Samples
Spring 2011
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